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A comprehensive study of the luminescence properties of cadmium pigments was undertaken to determine whether these properties could be used for in situ identification and mapping of the pigments in paintings. Cadmium pigments are semiconductors that show band edge luminescence in the visible range and deep trap luminescence in the red/infrared range. Emission maxima, quantum yields, and excitation spectra from the band edge and deep trap emissions were studied for sixty commercial cadmium pigments that span the color range from yellow to red (reflectance transition 470 to 660 nm). For paints containing cadmium pigments, luminescence from deep traps was more readily observable than that from the band edge, although the yield varied widely from zero to around 4.5%. Optimal excitation for emission is found to be in the visible for both pigments in powder form and mixed with a medium. The maxima of the deep trap emission shift with the band gap energy, providing a potentially useful way to assign pigment type even when used in pigment mixtures. The usefulness of the results of the study on mockups was demonstrated by the mapping of cadmium pigments of different hues with the aid of calibrated luminescence imaging spectroscopy in a painting by Edward Steichen, entitled Study for 'Le Tournesol' (1920). Analysis of the luminescence image cube reveals at least six unique spectral components, associated with emission from white pigments, paint binder, and cadmium red and yellow pigments. The results were compared with those from X-ray fluorescence spectrometry (XRF) and fiber-optic reflection spectroscopy (FORS) and the results obtained on paint samples containing cadmium pigments. These results show that, when present, the emission from traps can be used as an analytical tool to identify cadmium pigments, to distinguish among cadmium sulfide, cadmium zinc sulfide, and cadmium sulfoselenide, and to map cadmium pigments, even in mixtures.